Separation of linear aliphatic monoolefins from hydrocarbons by distilling with a nitrile



pri w67 W. J. MAT-rox ETAL 3,32602 SEPARATION OF LINEAR ALIPHATIC MONOOLEFINS FROM HYDROCARBONS BY DISTILLING WITH A NITRILE Filed Aug. 29, 1963 A United States Patent() 3,312,602 SEPARATION F LINEAR ALIPHATIC MONO- OLEFINS FRGM HYDROCARBONS BY DES- TILLING WITH A NETRILE William Judson Mattox and Glen Porter Hamner, Baton Rouge, La., assignors to Esso Research and Engineerr ing Company, a corporation of Delaware Filed Aug. 29, 1963, Ser. No. 305,397 11 Claims. (Cl. 203-53) This invention relates to the separation of hydrocarbons by means of distillation. More particularly it relates to a process for the separation of linear aliphatic olens from a mixture thereof with branched and cyclic mono-oleins, dioleins, and aromatics by azeotropic distillation using certain nitriles as a vapor entrainer.

At the present time there is a great amount of interest in the technical art with respect to the production of linear olens. In such production there are two principal routes to the linear olefins, viz., aluminum alkyl growth and wax cracking. It is with the latter method that the instant invention is concerned. Heretofore, it has been found, however, that the quality of such wax cracked olefins is inferior to the growth olens. Inasmuch as olen quality is directly related to the quality of the wax feed and to the cracking severity, diolefins, both conjugated and non-conjugated, are generally inherent at practical cracking severity levels. Further, aromatics and cyclic mono-olefins, resulting from cyclic structures in the wax feed, are also present. Hence, the problem of purifying wax cracked olefins is found to be dilicult in that it is necessary to remove impurities which are isomers and have boiling points which are similar to the desired product. The usual methods of separation employed, such as extractive distillation, solvent extraction, and adsorption are either inoperable, economically prohibitive, or of poor eflciency when oleins of relatively long chain length, e.g., six or more carbon atoms, are employed.

It is an object of the present invention therefore to provide a process for the separation of linear aliphatic olens from a mixture thereof with branched and cyclic mono-olens, diolens, and aromatics.

Another object of the present invention is to provide a process for separating Cs-Czo linear aliphatic olefins from a mixture thereof with branched and cyclic monoolefins, diolens and aromatics of similar boiling points by distillation methods.

Still another object of the present invention is to provide such a process which is economically feasible and will achieve a degree of purification of wax cracked oleiins which is at least the equal of the purity of alkyl growth olens.

Still other objects and advantages of the present invention will be realized from the following disclosure.

The present invention provides a means of separating linear aliphatic olens from mixtures thereof with corresponding branched and cyclic mono-olens, diolefins, and aromatics by distilling said mixture with a nitrile of the general formula R(Ci\I)n wherein n is 1 or 2 and R is an aliphatic hydrocarbon radical or an aliphatic hydrocarbon radical in which part of the hydrogen has been replaced with a'substituent group containing oxygen, halogen, or nitrogen, or other substituent groups containing one or more of these elements, said nitrile being em- ICC ployed as anazeotrope entrainen'distillingotf an azeotrope comprising a linear'aliphaticolen-nitrile heterogenous azeotrope, and removing the linear aliphatic olefin fraction from said entrainer. Examples of the nitrile substituent groups referred to above include hydroxyl, carbonyl, oxy, imino, and amino radicals and liuorine and chlorine atoms.

While the process of the present invention is applicable to any mixture of linear aliphatic olens with branched and cyclic mono-oleiins, dioleiins, and aromatics, the mixtures .shown herein are by-products of wax cracked petrolatum feedstocks. Thisis merely illustrative and not intended in any way to limit or restrict this invention. it must be pointed out, however, that in View of the general inferiority of the quality of Wax cracked olefins as hereinbefore mentioned, the fact that such wax cracked olens are effectively purifiedv is an outstanding advantage of the present process. Thus, the present invention is preferably applicable to mixtures of hydrocarbons having from 6 to 20 carbon atoms, and especially applicable to mixtures of hydrocarbons having from 7 to 16 carbon atoms, regardless of the source of the mixture.

The difficulties vinvolved in obtaining an efficient separation of the above discussed mixtures will be realized by a consideration of the boiling points of each of the components of one of the mixtures in question.` For example, at standard atmospheric pressure representative components boiling in the range of a C8 wax cracked olen have normal boiling points as presented in the following tabulation:

Boiling peint, F.

Component Octene-l 248.5 1,3-dimethylcyclohexene 25 5-25 9 4,4-dimethylcyclohexene 248-25 2 2,4-dimethylcyclohexene 264 3,3-dimethylcyclohexene 246 1,4-octadiene 232.2 1,5-octadiene 248 l,7octadiene 243 2,6-octadiene 25 6.1 2,5 dimethyl-2,3hexadiene 246-253 4-ethyl-1,4hexadiene 2752.1 Ethylbenzene 277.1

The separation is, however, evenmore diicult than would be anticipated even in view of the above close boiling points, inasmuch as constant-boiling mixtures are often formed between components of the mixture.

It is easily recognizable, therefore, that the choice of the proper nitrile entraining agent employed-in the process is a critical feature of the present invention. The choice of entraining agent is .important primarily with regard to its ability to form a practical nitrile-linear aliphatic olefin azeotrope. Further, the nitrile-linear monoolen azeotrope will preferably have a boiling point below that of the linear mono-olefin per se or the mixture or fraction from which such olen is to be separated. In addition, the relative miscibility of the nitrile is important in permitting entrainer recovery by simple means. Hence, it is preferable that the nitrile will also be at least partially immiscible with the product mono-olenat or about ambient temperatures so that upon-the cooling and condensation of the distillate a phase separation will Patented Apr. 4, 1967 "'azeotrope will preferably have be effected which yields essentially a nitrile layer and a hydrocarbon layer. Upon such separation, the nitrile layer is then suitable for recycle.

Accordingly it has been found that certain aliphatic nitriles possess the above qualities which mark their utility as entraining agents in the distillation of the closely boiling hydrocarbon components of the present invention. Broadly, these nitriles have the general formula:

moron wherein nis 1 or 2 and Ris a hydrocarbon radical having from 1 to 4 carbon atoms or a hydrocarbon radical having from 1 to 4 canbon atoms in which part of the hydro- 'gen has been replaced with oxygen, halogen, or nitrogen or other substituent groups containing one or more of these elements. lExamples of thev nitrile substituent groups referred to above include hydroxyl, carbonyl, oxy, imino, and amino radicals and uorine and chlorine atoms. Suitably, from 0.1 to'lO volumes of nitrile entraining agent are employed per volume of total feed mixture with 0.2'to 4 volumes of nitrile being preferably employed. The following are illustrative, but non-limiting examples of nitriles suitable for use in olefin purification process of the present invention.

Entraining agent: Boiling point, F.

Acetonitrile i 179 Propionitrile 207 Butyronitrile 244 Isobutyronitrile 219 Z-butenenitrile 244-246 3-butenenitrile 246.0 Methoxyacetonitrile 248 Malononitrile 428 Y Suiccinonitrile 512 Fluoroacetonitrile 176 Chloroacetonitrile 259 Trichloro acetonitrile 187 3-chloropropionitrile 3 5 2 3 ethoxypropionitrile 3 43 Iso-propoxypionitrile 3.7 4 3 -chlorobutyronitrile 3 86 3 -hydroxypropionitrile 442 2-chloro-2-methyl-propionitrile 241 As hereinbefore stated, the nitrile-'linear mono-olefin a boiling point below that f the linear mono-olefin per se or the mixture from which the mono-olefin is to be separated. By suitable choice of nitrile, therefore, an azeotrope of sufficiently low boilingr point can be obtained with the mono-olens to permit their separation from the herein undesirable hydrocarbons, i.e., branched and cyclic mono-oleiins, dioleiins, and aromatics in conventional distillation type equipment.

The preferred nitriles are the lower members of the acetonitrile series and the lower homologues of such series having up to about 4 carbon atoms in the chain. It has been found that with regard to the lighter linear monoolefins, e.g. C-CB linear mono-olens, that acetonitrile itself is particularly advantageous as an entraining agent in that it displays an effectiveness markedly above its homologues. With regar-d to the heavierlinear monooleins, eig. Cg-CZU linear mono-olefins, it is found that another group of nitriles is preferred, these nitriles being the chlorinated and hy-droxylated lower nitriles and derivatives containing up to aboutA4 carbon atoms. Monochloroacetonitrile, especially with C9-C12 linear monoolens, and 3-hydroxypropionitrile, especially with C12- Czo linear mono-olens, have been found to possess surprising superiority. Similarly it has been found that with the C15-C20 linear mono-olefins, malononitrile and succinonitrile are preferred entraining agents.

The nitrile entraining agents of the instant invention may be used alone or in multicomponent mixtures of suitable nitriles. In addition, it is sometimes preferred to form ternary azeotropes in the linear mono-olefin purification distillation by employing a `second or additional component 'in conjunction with the nitrile. Illustrative of suitable components which azeotrope with the feed to be purified and some of the nitriles are: alcohols, ketones, esters, ethers halogenated hydrocarbons, water, and the like. illustrative of such a ternary azeotrope is a crude C3 olen-water-acetonitrile azeotrope.

The preferred form of the invention involves its application to a continuous process and such form is illustrative in the FIGURE. For purposes of illustration, a C8 olefin cut is employed as feed and acetonitrile is employed as entraining agent. Y

Referring to thev figure, the C8 olefin cut, most probably obtained from the steam crackin-g of petrolatum, consisting of a mixture of linear mono-olefins, cyclic monoolefins, conjugated diolens, non-,conjugated diolefins,'and aromatics is fed from `storage tank 1 through line 11 preferably to dehydrating still 3. The base of this c-ontinuous column is conventionally heated which results in the removal of hydrocarbon-water azeotropes through vapor lines 12 and condenser 4 to decanter S. After phase separation the water layer is removed through line 14 and A the upper hydrocanbon layer 1s returned to reflux through line 15 to dehydrating still 3. The dehydrated olefinic feed is removed from the base of the still through line 16 and is fed through line 16 to separation still 6. In this column, the -olefinic feed mixture is contacted with from 1.2 to 1.8 volumes of acetonitrile per volume oftfeed, said acetonitrile having been previously pumped into the column from acetonitrile storage tank 2 through lines 17 and 16. The more volatile acetonitrile-linear monoolefin azeotropes are removed from the top of the column Ythrough vapor line 18 and are condensed in condenser 7. The condensate therefrom ows through line 19 into decanter 8, where Iit separates into an upper CB linear m-ono-olein-rich Vphase and a lower acetonitrile-rich phase. The mono-olefin-rich phase is withdrawn from the system through line 20 to receiver tank 9 and the lower acetonitrile layer is-returned as reux to column 6 throughy line 21. To maintain proper reflux on the column, a portion of the mono-oleiin-rich phase may also be returned to the column thro-ugh line 22. inasmuch as acetonitrile content of the linear mono-olefin-rich phase contained in the receiver tank 9 may sometimes reach a content as high as about 5%, in such cases separation of the acetonitrile from the linear mono-olefin is desirable. Separation is suit-ably effected by water addition to the receiver tank 9 with subsequent two-phase formation of a substantially pure linear mono-olefin phase and an aqueous acetonitrile phase. These phases are separated in a known manner, e.g. decantation; the acetonitrile being recovered from the bottom phase for further use and the olefin phase being withdrawn to further processing, if desired.

The amount of acetonitrile in the column is limited to the extent that a separation between the acetonitrile-linear mono-olefin azeotropes from the feed mixture is effected in the lower trays, and the raffinate resulting from such separation, containing little -or no acetonitrile, is removed through line 24 from the base` of the column and collected in receiver tank 1t?. To compensate for minor losses of acetonitrile by partial solution in t-he upper layer of decanter 8, acetonitrile may be added intermittently from storage tank 2 through lines 17 and 16. In case of incomplete water removal in dehydating still 3 a slow bleed of acetonitrile-water mixture can be taken from the lower layer of decanter 8 through line 23 to maintain anhydrous conditions in column 6.

As hereinbefore disclosed, the acetonitrile can also in some instances, depending on the olenic impurities, be used as an aqueous azeotrope. Usage of this azeotrope would obvi-ate the need of dehydrating still 3 in the figure E and would permit thelbase of separation column 6 to operate at a lower temperature.

6 of the three runs along with theuntreated feed is surnmarized in the following table.

TABLE I.-AZEOTROPIC DISTILLATION OF Cs OLEFIN FRACTION WITH NITRILES C@ Run Run Run Feedl No. 1 No.2 No. 3

Nitrile Aceto- Propioiso-Butyro- Boiling Point, 179 207 219 VOL/Vol. of Hydrocarbon 1. 7 1. 0 3.0 Azeotrope:

Boiling Point, F 171-172 199-201 213-214 Hydrocarbon, Vol. percent 40. 4 43. 6 40.1 Octene Concentrate:

Vol. Percent of Feed 2' 71-74 74 74 Silica Gel Separation Anal.:

Monoolens:

Li'lear 75. 5 92. 6 84. 4 86.1 Cyclic 7. 3 3. 9 7. 3 4.7 Dioletins:

Conjugatcd 2. 5 0. 04 0. 7 0.6 Non-eonjugated- 11. t) 3. 3 7. 2 8. 1 Aromatics 3. 2 0. 01 0. 1 0. 2 Saturates 0.5 0.2 0.3 0.3 Oletms:

1. 4 0.01 5, e 0.5 92. 4 99. 97 93. 9 99. 5 6. 2 0.02 0. 5 Trace 1.11 1.09 1.11 1.07

1 Average of three analyses. 2 From refractive index and bromine number plots. 2 Analysis of 73% of purified product recovered between 20 and 74% overhead.

The invention can also be applied to a batchwise technique. In this case, a mixture of the acetonitrile and the C8 olefin feed mixture is charged to the kettle of a batch still. The overhead product from the column is condensed and the liquid phases separated in a decanter. The lower acetonitrile layer is returned to the column as rellux, together with suicient upper layer to maintain proper reux on the system. A stream from the upper layer, consisting essentially of C8 linear mono-olens, is also withdrawn to the product tank. When separation of the linear mono-olefin component by this method is essentially cornplete, the reux and product system is changed so that all the upper layer is returned as reliux to the column and all the lower layer is withdrawn to a second product tank. When the acetonitrile has been stripped from the system in this manner, the still can be shut down and the kettle liquid consisting of rallnate can be pumped from the systern. The acetonitrile entrainer, in the second product tank can then be returned to the system for reuse with the next batch.

The following specific examples will serve to further illustrate the present invention and are not to be construed as limiting the present invention.

Example I In a series of three runs a C8 olen cut obtained in the stream cracking of petrolatum was mixed with acetonitrile (Run No. 1), propionitrile (Run No. 2), and isobutyronitrile (Run No. 3), and distilled at atmospheric pressure in a l-inch, t0-plate Oldershaw column. The resulting distillate` fractions, comprising the acetonitrile- CTI From the above it is seen that a feed containing a total of 82.8% mono-olens was upgraded to a total monoolen content of 96.5%, 91.7%, and 90.8% respectively.

Example Il In a manner similar to Example I, a C10 olelin cut was mixed with acetonitrile (Run No. l), and chloroacetonitrile (Run No. 2), and distilled at atmospheric pressure. The resulting fractions were analyzed also in a similar manner with the data being compared in the table below:

TABLE 11.-AZEOTROPIC DISTILLATION OF A C10 OLEFIN FRACTION WITH NITRILES Cm Feed Run Run No. 2

Nitrile Aceto- Chloro-aceto- Boiling P 179 259 Vol/Vol. of Hydreearb 6. (l 2. 8 Azeotrope:

Boiling Point, F 178-179 25.2253 Hydrocarbon, Vol. percent 3.3 32. 9 Decene Concentrates:

Vol. Percent ol Feed 1 28 74 Silica Gel Separation Anal:

Mono-olefins:

Linear 86. 5 94. 6 95. 6 Cyclic 3. 7 2. 7 1. 8 Diolens:

Conjugated 0. 3 0.2 0.01 Nou-eonjugated 5. 6 1.4 2. 3 Aromatics 3. 5 0. 3 Trace 0. 4 0.8 0.3

99 98 v99 1 l 1 0 1 0 0 O 0 0. 9 Trace 94. 7 94. 4 96. 8 5. 2 4. 6 3. 2 C12- 0. CH3/Mol 1 From refractive index and bromine number plots.

' method of the present invention, to that of Example I were made on a crude C8 7 Example IIl TABLE IIL-ZEOIROIIC DISTILLATION OF C1 OLEFIN RACTION WITH ACETONIT RILE Feed Azeotropic Distillnt-ion Azeotrope:A

Boiling Point, F 156-160 Hydrocarbon, Vol. percent; 61. Heptene Concentrate:

Vol. percent of Feed (l) 70 Silica Gel Separation Analysis:

Mono-olens:

Linear 74. 2 90. 2 Cyclic 9. 7 2. 4 Dioleins:

Conjugated 1. S 0.1 Non-conjugated 11. 0 8 Aromatics 2. 8 0. 1 Saturates 0. 5 0. 4 Olefins:

Type I 88 A 95 Type IL- 5 3 Type I 4 2 Type IV 3 0 Carbon No., percent:

C0 Trace 1. 5 C7 87. 7 98. 4 Cs... 12. 3 0.1 CH3/Mol- 1. 09 1.07

1 From refractive index and bromine number plots.

Example 1V In order to determine the effectiveness of a ternary nitrile-water-linear olefine azeotrope in the purification two distillations similar olefin cut. The entrainer employed in Run No. l was acetonitrile (B.P. 179 F.) and the entrainer of Run No. 2 `was 82.6% acetonitrile'17.4% water (B.P. 169 F.). The boiling point of the azeotropes distilled in each run was determined as Well as'the composition of both layers of said distillate. The following tabulation summarizes hydrocarbon-entrainer distributions for the acetronitrile-octene Yazeotrope in comparison with the distribution for the ternary acetonitrile-water-ocetene azeotrope.

\ TABLE IV Run No. 1 Run No. 2

Azeotrope:

Boiling point, F 171-172 161 Upper layer (vol. percent) 28.9 44. 7

Percent hydrocarbon 93. 5 94. 0

Percent entrainer 6. 5 6. 0

Lower layer (vol. percent) 71.1 55.3

Percent hydrocarbon 20.3 5. 5

Percent entrainer 79. 7 94. 5

Total azeotrope, percent hydrocarbon- Upper layer 27. 0 42.

Lower layer. 3.

Total 41.4

The ternary water-containing azeotrope of Run No. 2 has a lower boiling point and contained 3.6% more hydrocarbon than the acetonitrile-octene azeotrope. Also of significance is the decreased proportion of hydrocarbon in the nitrile layer (5.5%) obtained upon condensing the distillate, thereby resulting in a material more suitable for recycle in a continuous distillation. This system is particularly useful in purifying linear olen fractions of low diolen content. It will usually be preferred with dioleincontaining mixtures to employ an essentially anhydrous entrainer.

, each contains an attractive 8 Example V Succinonitrile and 3-hydroxypropionitrle were employed as entrainers for hexadecene-l contained in a C16 olefin fraction obtained in the steam cracking of petrolatum. Properties of these azeotropes are summarized in the following tabulation.

Each of these azeotropes has a boiling point appreciably lower than the pure hydrocarbon (27 F. for succinonitrile and 67 F. for 3-l1ydroxypropionitrile) and level of hydrocarbon, both qualities of practical entraining agents.

It is to :be understood that the invention is not to be limited to the exact details of operations shown land described, as obvious modifications and equavalents will be apparent to one skilled in the art, and the invention is therefore to be limited only to the scope of the appended claims.

vWhat is claimed is:

1. The method of separating linear aliphatic monooleflns from mixtures thereof with close boiling corresponding branched and cyclic mono-olefins, diolens, and aromatics which comprises distilling said mixture with a nitrile of the general formula:

wherein n is an integer of 1 to 2 and R is selected from the group consisting of C1 to C4 aliphatic hydrocarbon radicals and C1 to C4 aliphatic hydrocarbon radicals in which at least one hydrogen atom at least one substituent group containing an atom selected from the group consisting of oxygen, halogen and nitrogen, said nitrile being employed as an azeotrope entrainer, distilling off an azeotrope comprising a linear aliphatic monoolein nitrile heterogenous azeotrope, and removing the linear aliphatic monoolefin fraction from said entrainer.

2. The method of claim 1 in which from 0.1 to 10 volumes of said nitrile are employed per volume of mixture.

3. The method of claim 1 in which water is used as an additional entrainer component with said nitrile.

4. The method of claim 1 in which the linear aliphatic monoolen is a Cg-Czo monoolen.

5. The method of separating CG-C linear aliphatic monoolens from mixtures thereof with corresponding branched and cyclic mono-olens, dioleflns, and aromatics which comprises distilling said mixture with a nitrile azeotrope entrainer of the general formula:

RCN

wherein R is a C1-C4 aliphatic hydrocarbon radical, distilling off an azeotrope comprising a C-Cs linear monoolein-nitrile heterogenous azeotrope and removing the C6-C8 linear monooletin fraction from said entrainer.

6. The method of claim 5 in which from 0.2 to 4 volumes of said nitrile are employed per volume of mixture.

7. The method of separating C6-C20 linear aliphatic monooleins from mixtures thereof with corresponding branched and cyclic mono-olefins, and aromatics which comprises distilling said mixture with an azeotrope entrainer consisting of water and a nitrile of the general formula:

wherein n is 1 or 2, R is a Cl-C4 aliphatic hydrocarbon radical, distilling'oif an azeotrope comprising a C6-C20 has been replaced by l linear monoolen-nitrile heterogenous azeotrope and removing the C6-C20 linear monoolelin fraction from said entrainer.

8. The method of separating CS-C linear aliphatic monoolefins from mixtures thereof with corresponding branched and cyclic mono-oleiins, dioleiins, and aromatics which comprises distilling said mixture with from l to 5 volumes of an acetonitrile azeotrope entrainer per volume of mixture, distilling olf an azeotrope comprising a C-Cg linear monoolefin-acetonitrile heterogenous azeotrope and removing the CG-C linear monoolen fraction from said entrainer.

9. The method of separating C9-C12 linear aliphatic monoolens from mixtures thereof With corresponding branched and cyclic mono-olefins, diolens, and aromatics Which comprises distilling said mixture with from 1 to 5 volumes of a chloroacetonitrile azeotrope entrainer per volume of mixture, distilli-ng off an azeotrope comprising a C9-C12 linear monooleiin-chloroacetonitrile heterogenous azeotrope and removing the Cg-Clg linear monooleiin fraction from said entrainer.

10. The method of separating C12-C20 linear aliphatic monooleiins from mixtures thereof with corresponding branched and cyclic mono-olens, dioleins, and aromatics which comprises distilling said mixture with from l to 5 volumes of B-hydroxypropionitrile azeotrope entrainer per volume of mixture, distilling off an azeotrope compris- References Cited by the Examiner UNITED STATES PATENTS 2,679,472 5/1954 Tooke n 203-60 2,842,484 7/1958 Fleck 203-60 2,848,387 8/ 1958 Glazier et al 203-60 3,008,880 11/1961 Dodge et al 203-60 3,087,866 4/1963 Burch 203-53 FOREIGN PATENTS 548,733 10/ 1942 Great Britain.

NORMAN YUDKOFF, Primary Examiner. WILBUR L. BASCOMB, JR., Examiner. 

1. THE METHOD OF SEPARATING LINEAR ALIPHATIC MONOOLEFINS FROM MIXTURES THEREOF WITH CLOSE BOILING CORRESPONDING BRANCHED AND CYCLIC MONO-OLEFINS, DIOLEFINS, AND AROMATICS WHICH COMPRISES DISTILLING SAID MIXTURE WITH A NITRILE OF THE GENERAL FORMULA: 